Reactive coalescents

ABSTRACT

Compounds useful as reactive coalescents and methods of improving the stability of reactive coalescents are disclosed. A process for the preparation of low molecular weight polymers which are also useful as reactive coalescents is also disclosed.

This application claims priority to provisional application No.60/042,725 filed Apr. 8, 1997.

This invention relates to compounds which are useful as reactivecoalescents, methods of improving the stability of reactive coalescents,and a process of preparing low molecular weight polymers which areuseful as reactive coalescents.

Water based polymers having a low glass transition temperature (“Tg”)can be formulated into coatings without plasticizers. These coatingsoften have inadequate hardness for many applications. Many applications,such as gloss and semigloss paint formulations, require the propertiesof a hard polymer, i.e. a polymer with a Tg significantly above theambient temperature. To meet these needs, a volatile coalescent orplasticizer is typically used to achieve film formation. The use ofthese volatile solvents in coatings is coming under scrutiny due topollution and odor problems.

Attempts have been made to use “reactive coalescents”. Reactivecoalescents are compounds which aid in film formation similar to theconventional coalescent but are non-volatile and react to become part ofthe final coating.

U.S. Pat. No. 4,141,868 discloses the use of dicyclopentenyloxyethylmethacrylate (“DCPOEMA”) as a reactive coalescent. Vinyl reactivecoalescents are reactive coalescents which contain a vinyl group.DCPOEMA, dicyclopentenyloxyethyl acrylate (“DCPOEA”), dicyclopentenyloxyacrylate (“DCPOA”), and dicyclopentenyloxy methacrylate (“DCPOMA”) areexamples of vinyl reactive coalescents.

Despite the disclosure, there is a continuing need for stable reactivecoalescents for use in coating compositions.

We have surprisingly found that stable reactive coalescents for use incoating compositions can be obtained by altering the structure of thereactive coalescent or adding an inhibitor to the reactive coalescent.

In a first aspect, the present invention provides compounds of formulaI:

Wherein:

R=—(CH₂)_(n)R¹, —(CH₂)₂O(CH₂)₂OH, —(CH₂CH₂O)₂(CH₂)₃OH, —CH₂CH₂OCOR²,—(CH₂)₂O(CH₂)₂O(CH₂)₃CH₃, —CH₂CH(CH₃)—OH, —CH₂CH₂OCO(CH₂)₄COOR³,dicyclopentenyloxyethane;

R¹ is selected from H, OH and CH₃;

R²=(C₁-C₆) straight chain or branched alkyl;

R₃ is selected from CH₃ and dicyclopentenyloxyethane; and n=2 to 10.

In a second aspect, the present invention provides a process for thepreparation of polymers comprising:

providing a compound selected from the group consisting of DCPOEA,DCPOEMA, DCPOA, and DCPOMA;

providing a solvent selected from the group consisting of water,acetone, methanol, isopropanol, propionic acid, acetic acid, toluene,hexane, ethyl acetate, methylethyl ketone, dimethyl formamide,dimethylsulfoxide, and combinations thereof,

providing an initiator;

forming a reaction mixture by admixing the compound selected from thegroup consisting of DCPOEA, DCPOEMA, DCPOA, and DCPOMA, the solvent, andthe initiator; and

passing the reaction mixture through a heated zone wherein the reactionmixture is maintained at a temperature of at least 175° C. for from 0.1seconds to 300 seconds to form a liquid polymer with a number averagemolecular weight of from 450 to 10,000.

In a third aspect, the present invention provides a method of usecomprising:

providing an emulsion polymer;

providing a liquid polymer prepared from a compound selected from thegroup consisting of DCPOEA, DCPOEMA, DCPOA, and DCPOMA, the liquidpolymer having a number average molecular weight of from 450 to 10,000;

forming a coating composition by admixing the liquid polymer having anumber average molecular weight of from 450 to 10,000 with the emulsionpolymer; and;

applying said coating composition to a substrate wherein the coatingcomposition forms a continuous film on the substrate.

In another embodiment, the present invention provides a compositioncomprising:

from 1% to 25% of a vinyl reactive coalescent based on a weight reactivecoalescent to total weight of composition basis;

from 1 ppm to 10,000 ppm of an inhibitor selected from the groupconsisting of 4-methoxyphenol,4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy,4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, and di-tertiary butylnitroxyl, based on a weight inhibitor to total weight of compositionbasis; and

from 74% to 99% of an emulsion polymer based on a weight emulsionpolymer to total weight of composition basis.

In another embodiment, the present invention provides a method forimproving the stability of a vinyl reactive coalescent comprising:

providing an emulsion polymer;

passing the emulsion polymer through a diafiltration apparatus; and

charging the emulsion polymer which has been passed through thediafiltration apparatus with a vinyl reactive coalescent.

In another embodiment, the present invention provides a coatingcomposition comprising:

an emulsion polymer; and

a compound selected from the compounds of Formula I

 Wherein:

R=—(CH₂)_(n)R¹, —(CH₂)₂O(CH₂)₂OH, —(CH₂CH₂O)₂(CH₂)₃OH, —CH₂CH₂OCOR²,—(CH₂)₂O(CH₂)₂O(CH₂)₃CH₃, —CH₂CH(CH₃)—OH, —CH₂CH₂OCO(CH₂)₄COOR³,dicyclopentenyloxyethane;

R¹ is selected from H, OH and CH₃;

R²=(C₁-C₆) straight chain or branched alkyl;

R³ is selected from CH₃ and dicyclopentenyloxyethane; and n=2 to 10, anda liquid polymer prepared from a compound selected from the groupconsisting of DCPOEA, DCPOEMA, DCPOA, and DCPOMA, the liquid polymerhaving a number average molecular weight of from 450 to 10,000.

The inhibitors useful in this invention include hydroquinone (“HQ”),4-methoxyphenol (“MEHQ”), phenothiazine (“PTZ”), 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (“4-HT”), and4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, are available from AldrichChemical Company. Di-tertiary butyl nitroxyl is available from NovaMolecular Technologies, Lake Geneva, Wisconsin. The inhibitors aretypically used at levels of from 1 ppm to 10,000 ppm on a weightinhibitor to total weight of the composition basis. Preferred areinhibitor levels of from 100 ppm to 1,000 ppm. More preferred areinhibitor levels of from 200 ppm to 700 ppm.

The reactive coalescents of this invention are prepared by processesknown in the art. For example, direct esterification,transesterification or the use of acid halides may be employed toconvert alcohols to esters of this invention. Examples of compounds ofFormula I include, but are not limited to: dicyclopentenyloxyethylacetate, dicyclopentenyloxyethyl butyrate,dicyclopentenyloxy-2-(2-hydroxyethoxy)ethane, dicyclopentenyloxy-2-(2-butoxyethoxy)ethane, dicyclopentenyloxyhexanol,dicyclopentenyloxyhexane, dicyclopentenyloxybutane, dicyclopentenyloxy(2-methyl)propane, and 1,2-bis (dicyclopentenyloxy)ethane.

The low molecular weight polymers of this invention may be useful asreactive coalescents, and may be prepared by conventional techniques,such as solution or emulsion polymerization, which are well known in theart. The low molecular weight polymers may also be prepared by the hightemperature, low residence time process of this invention. In theprocess of this invention, a reaction mixture is formed by combining atleast one compound selected from DCPOEA, DCPOEMA, DCPOA, and DCPOMA andoptionally, compatible monomers with a solvent and an initiator.Suitable solvents include, but are not limited to water, acetone,methanol, isopropanol, propionic acid, acetic acid, toluene, alkanessuch as hexane; esters such as ethyl acetate; methylethyl ketone,dimethyl formamide, dimethylsulfoxide, and combinations thereof. Theprocess of this invention may be run in the absence of solvent.

Initiators are compounds which initiate the polymerization of monomers.Suitable initiators for the present invention are any conventionalinitiators. Among the suitable initiators that may be used are thermalfree-radical initiators, such as hydrogen peroxide, certain alkylhydroperoxides, dialkyl peroxides, persulfates, peresters,percarbonates, ketone peroxides and azo initiators. Specificfree-radical initiators include, for example, hydrogen peroxide,tert-butyl hydroperoxide, di-tert-butyl peroxide, ammonium persulfate,potassium persulfate, sodium persulfate, tert-amyl hydroperoxide andmethyl ethyl ketone peroxide. The free-radical initiators are typicallyused in amounts of 0.5 to 25% based on the total monomer weight.

Redox initiator systems may also be used. Redox initiator sytems includereducing agents, for example, sodium bisulfite, sodium sulfite,hypophosphites, phosphites, isoascorbic acid, sodiumformaldehyde-sulfoxylate and hydroxylamines, used in conjunction withsuitable oxidizing agents, such as the thermal free-radical initiatorsnoted above. The redox initiator systems are typically used in amountsfrom 0.05 to 10%, preferably from 0.5 to 5%, based on the weight oftotal monomer. Combinations of initiators may be used.

The process of this invention is typically run at a temperature of from175° C. to 500° C. Preferred is a temperature of from 225° C. to 450° C.It is preferred to conduct the polymerization at a pressure of from1,000 to 5,000 pounds per square inch (“psi”), and more preferably atfrom 3,200 to 4,200 psi. By low molecular weight polymers is meantpolymers typically with number average molecular weights from 450 to10,000. Preferred are polymers with number average molecular weightsfrom 450 to 5,000. More preferred are polymers with number averagemolecular weights from 450 to 3,000.

Compatible monomers are monomers which are miscible with DCPOEA,DCPOEMA, DCPOA or DCPOMA. Compatible monomers include, but are notlimited to: methyl acrylate, ethyl acrylate, butyl acrylate,t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate,isobornyl methacrylate, styrene, vinyl toluene, methacrylic acid, methylmethacrylate, butyl methacrylate, isobutyl methacrylate, allylmethacrylate, lauryl methacrylate, and 2-ethylhexyl methacrylate.

The reactive coalescents are typically used at levels of from 1% to 25%on a weight reactive coalescent to total weight of composition basis.Preferred are reactive coalescent levels of from 2% to 20%. Morepreferred are reactive coalescent levels of from 5% to 15%.

This invention may be applied to any emulsion polymer. The preparationof emulsion polymers is known in the art, see for example U.S. Pat. No.5,346,954.

The following is a list of products used within this invention and theirsources:

Product Source Tamol ®165 Rohm and Haas Company Triton ®CF-10 UnionCarbide Drew ®ZV-22 Ashland Chemical Company RM-2020NPR Rohm and HaasCompany Ti-Pure ®R-706 DuPont Chemical Company Rhoplex ®EXP-3361 Rohmand Haas Company Scotch ®Tape Minnesota Mining and Manufacturing CompanyTamol ®731 Rohm and Haas Company BYK-22 BYK-Chemie GmbH GR-7M UnionCarbide Triton ®XN-45S Union Carbide

The following examples are intended to demonstrate the compounds andcompositions of this invention and their use as stable reactivecoalescents.

EXAMPLE 1 Improved Stability Of DCPOEMA

Reactive coalescents containing unsaturated vinyl groups can polymerizein the can due to residual impurities in the polymer. The poor stabilityof the coalescent manifests itself as loss of film forming properties ofthe formulated coating over time. DCPOEMA is a reactive coalescent whichcontains 100 ppm hydroquinone as purchased. Various inhibitor types andlevels were added to DCPOEMA prior to use in a coating composition. Thereactive coalescent and inhibitor mixtures were prepared prior to thecompositions by adding DCPOEMA to a fixed amount of solid gradeinhibitor. The mixtures were then post-added to a portion of a mastermix of paint 1. A portion of each sample was stored at 140° F. for 10days. The minimum film forming temperature (“MFFT”) was measured foreach sample. If the DCPOEMA was stable, the MFFT remained low whencompared to the control sample. If the DCPOEMA was unstable, the MFFTwas elevated when compared to the control. The DCPOEMA was considered tobe stable if the MFFT increased less than 5° C. after the sample wasstored at 140° F. for 10 days. The results of the tests are shown inTable 1.

Paint 1

A master paint formulation containing no coalescent was prepared asfollows:

18 g water, 1.61 g Tamol® 165, 0.50 g Triton® CF-10, 0.25 g Drew® ZV-22,

3.75 g RM-2020NPR, and 45.0 g Ti-Pure® R-706 were ground with a highspeed disperser for 15 minutes. To the mixture was added 131.27 gEXP-3361,

0.25 g Drew® ZV-22, 1.18 g RM202ONPR, and 40.25 g water with furthermixing.

Sample 1 was a control sample of Paint 1 with DCPOEMA, but no additionalinhibitor.

Sample 2 was prepared by combining 7.55 g of a mixture of 0.29 g ofsolid grade 4-HT dissolved in 57.71 g of DCPOEMA with 244.06 g of paint1.

Sample 3 was prepared by combining 7.55 g of a mixture of 0.60 g ofsolid grade 4-HT dissolved in 59.40 g of DCPOEMA with 244.06 g of paint1.

Sample 4 was prepared by combining 7.55 g of a mixture of 1.20 g ofsolid grade 4-HT dissolved in 58.80 g of DCPOEMA with 244.06 g of paint1.

Sample 5 was prepared by combining 7.55 g of a mixture of 2.37 g ofsolid grade 4-HT dissolved in 56.88 g of DCPOEMA with 244.06 g of paint1.

Sample 6 was prepared by combining 7.55 g of a mixture of 0.30 g of MEHQdissolved in 59.70 g of DCPOEMA with 244.06 g of paint 1.

Sample 7 was prepared by combining 7.55 g of a mixture of 0.60 g of MEHQdissolved in 59.40 g of DCPOEMA with 244.06 g of paint 1.

Sample 8 was prepared by combining 7.55 g of a mixture of 1.16 g of MEHQdissolved in 56.84 g of DCPOEMA with 244.06 g of paint 1.

Sample 9 was prepared by combining 7.55 g of a mixture of 2.42 g of MEHQdissolved in 58.08 g of DCPOEMA with 244.06 g of paint 1.

Sample 10 was prepared by combining 7.55 g of a mixture of 0.24 g of HQdissolved in 57.71 g of DCPOEMA with 244.06 of paint 1.

Sample 11 was prepared by combining 7.55 g of a mixture of 0.60 g of HQdissolved in 59.40 g of DCPOEMA with 244.06 g of paint 1.

Sample 12 was prepared by combining 7.55 g of a mixture of 1.19 g of HQdissolved in 58.31 g of DCPOEMA with 244.06 g of paint 1.

Sample 13 was prepared by combining 7.55 g of a mixture of 0.31 g of PTZdissolved in 61.69 g of DCPOEMA with 244.06 g of paint 1.

Sample 14 was prepared by combining 7.55 g of a mixture of 0.61 g of PTZdissolved in 60.39 g of DCPOEMA with 244.06 g of paint 1.

Sample 15 was prepared by combining 7.55 g of a mixture of 1.21 g of PTZdissolved in 59.29 g of DCPOEMA with 244.06 of paint 1.

The MFFT Test was Performed as Follows:

Scotch® Tape biaxially oriented polypropylene was placed on an ICI SheenMFFT Bar SS-3300. Samples were drawn down over the tape using a 1 inchcube Sheen Film Applicator with a gap size of 75 micron. After 60 to 90minutes, the MFFT was read as the point where the film becomescontinuous and not cracked.

The Low Temperature Film Formation Test was Performed as Follows:

Samples were painted by brush onto white pine boards. The paint wasapplied in strips perpendicular to the length of the board. Each samplewas weighed to provide a spread rate of 41.8 m²/liter. The paintedboards were dried for 24 hours at 40° F./70% relative humidity. Amagnifying glass was used to determine the degree of cracking in thepaint film. The degree of cracking was reported according to thefollowing scale:

10=none, 9=trace, 8=trace/slight, 7=slight, 6=slight/moderate,5=moderate, 4=moderate/heavy, 3=heavy, 2=heavy/very heavy, 1=very heavy.

A score of 10 is considered to be passing.

TABLE 1 Inhibitor MFFT (° C.) Sample Inhibitor Level Initial 10 Days @140 F. 1 None None 5.1 >18 2 4-HT  625 ppm 5.1 5.6 3 4-HT 1250 ppm 5.35.6 4 4-HT 2500 ppm 5.3 5.6 5 4-HT 5000 ppm 5.3 5.6 6 MEHQ  625 ppm 4.95.6 7 MEHQ 1250 ppm 4.9 6.4 8 MEHQ 2500 ppm 4.9 7.6 9 MEHQ 5000 ppm 4.57.6 10 HQ  625 ppm 7.8 >18 11 HQ 1250 ppm 8.0 >18 12 HQ 2500 ppm 9.2 >1813 PTZ  625 ppm 8.0 >18 14 PTZ 1250 ppm 7.8 >18 15 PTZ 2500 ppm 9.2 >18

The results demonstrate that 4-HT and MEHQ improve the stability ofDCPOEMA. HQ and PTZ did not improve the stability of DCPOEMA.

EXAMPLE 2 The Level of Inhibitor Required to Stabilze DCPOEMA

The level of 4-HT required to provide stability in commercial polymerswas evaluated. Samples were prepared by adding 4-HT to latex, this wascalled a modified latex. The modified latex was then formulated intopaints. Sub-samples of Samples 16-19 were stored at 140° F. for 30 days.Sub-samples of Samples 20-23 were stored at 140° F. for 10 days. TheMFFT was measured for each Sample. The results are shown in Tables 2 and3.

Paint 2

Paint 2 was prepared for Samples 16-19 as follows: 72 g water, 12 gTamol® 731, 2 g Triton® CF-10, 2 g BYK 22, 20 g RM-2020NPR, and 300 gTi-Pure® R-706 were ground with a high speed disperser for 15 minutes.To the mixture was added 106.32 g water, 2 g GR-7M, 544.14 g modifiedRhoplex® AC-261, 26.84 g DCPOEMA, 2 g BYK-22, and 10 g water withfurther mixing.

Paint 3

Paint 3 was prepared for Samples 20-23 as follows: 72 g water, 12 gTamol® 731, 2 g Triton® CF-10, 2 g BYK 22, 20 g RM-202ONPR, and 300 gTi-Pure® R-706 were ground with a high speed disperser for 15 minutes.To the mixture was added 106.32 g water, 2 g GR-7M, 544.14 g modifiedRhoplex® EXP-3361, 26.84 g DCPOEMA, 2 g BYK-22, and 10 g water withfurther mixing.

Sample 16 was a control paint 2 with DCPOEMA, but no additionalinhibitor.

Sample 17 was prepared by combining 3.84 g of a 5% aqueous 4-HT mixturewith 961.85 g of paint 2.

Sample 18 was prepared by combining 7.68 g of a 5% aqueous 4-HT mixturewith 961.85 g of paint 2.

Sample 19 was prepared by combining 11.50 g of a 5% aqueous 4-HT mixturewith 961.85 g of paint 2.

Sample 20 was prepared by combining 20.24 g of a 5% aqueous 4-HT mixturewith 2,929.60 g of paint 3.

Sample 21 was prepared by combining 26.99 g of a 5% aqueous 4-HT mixturewith 2,946.35 g of paint 3.

Sample 22 was prepared by combining 43.50 g of a 5% aqueous 4-HT mixturewith 2,949.10 g of paint 3.

Sample 23 was prepared by combining 58.10 g of a 5% aqueous 4-HT mixturewith 2,963.70 g of paint 3.

TABLE 2 Low Temperature Film Formation Sample 4-HT Level Equilibrated 30Days @ 140 F. 16   0 ppm 10 1 17  400 ppm 10 10 18  800 ppm 10 10 191200 ppm 10 10

TABLE 3 MFFT MFFT Sample 4-HT Level Initial 10 Day @ 140 F. 20  750 ppm9.5° C.  9.5° C. 21 1000 ppm 7.9° C. 10.2° C. 22 1600 ppm 8.3° C. 10.9°C. 23 2100 ppm 9.3° C. 10.9° C.

Tables 2 and 3 demonstrate that levels as low as 400ppm of 4-HT wereeffective at stabilizing the reactive coalescent.

EXAMPLE 3 Diafiltration of Coating Compositions

Another approach to stabilizing the DCPOEMA in coating compositionsinvolves diafiltration of the polymer to remove residual water solubleimpurities. During the diafiltration process, the aqueous phase of thepolymer is replaced with clean deionized water. The coating compositionswere prepared according to Paint 1 except JH-2479 was substituted forEXP-3361. The preparation of JH-2479 was as follows (materials arelisted in Table 4):

A stirred reactor containing 1,283 g of deionized (D.I.) water washeated to 88° C. under nitrogen. To this was added 7.2 g of sodiumcarbonate dissolved in 85 g of DI water followed by a solution of 3.6 gof sodium persulfate in 20 g of DI water and 49 g (solids basis) of a 60nm seed latex with 80.5 g of DI water. The temperature was allowed tofall to 85 ° C. The feed of monomer emulsion (“ME”) #1 was started andfed to the reactor over 67 minutes. At the same time a feed of asolution of 1.8 g of sodium persulfate in 100 g of water was started tothe reactor. The reaction temperature was held at 85° C. At thecompletion of the ME #1 feed the cofed sodium persulfate feed wasstopped and the reaction mixture was held at temperature for 15 minutes.The ME #1 feed line was flushed to the reactor using 40 g of DI water.Then the feed of ME #2 was started and fed to the reactor over 103minutes. The cofeed sodium persulfate feed was restarted at the start ofthe ME #2 feed. At the completion of both feeds the reactor was held attemperature for 30 minutes and the feed lines flushed to the reactorwith 40 g of DI water. The reaction mixture was cooled to 55° C. and0.01 g of iron sulfate heptahydrate, 0.5 g of 70% aqueous t-butylhydroperoxide, and 0.6 g of isoascorbic acid were added in a total of 25g of DI water. The reaction mixture was cooled to room temperature andthe pH adjusted to 9.0 using ammonium hydroxide.

The final product had a solids content of 45.9%, particle size byBrookhaven BI-90 (light scattering) of 190 nm., and a Brookfieldviscosity (LVT viscometer, 30 rpm, 25° C.) of 60 cps.

TABLE 4 ME #1 ME #2 DI water 121.3 g 260.0 g Triton ®XN-45S  15.8 g 25.4 g Butyl Acrylate 326.7 g 381.2 g Methyl Methacrylate 388.5 g 517.3g Allyl Methacrylate  7.3 g Methacrylic Acid  3.6 g  27.2 g Acetoacetoxy163.4 g Methacrylate

The microfiltration unit was an Industrial Maximate manufactured byFiltron. The main feed tank was a 5 gallon polypropylene tank. Therecirculating pump was an M-1 diaphragm pump manufactured by Wildon. Anin-line water filter was positioned after the pump. The microfiltrationmembrane was an Omega series modified polyether sulfone. The molecularweight cut-off for the membrane was about 30,000. The channel size ofthe membrane was 40 mil. The solution being filtered was recirculatedfrom the main feed tank to the microfiltration membrane and back to themain feed tank by the pump. A 2.5 gallon polypropylene carboy was usedto collect the permeate as it was produced on the other side of themicrofiltration membrane. A feed pump manufactured by Fluid MeteringPump Inc. was used to add deionized water to the main feed tank tomaintain the fluid volume in the tank during filtration.

A solution was prepared by mixing 3,500 g of JH-2479 with 3,500 grams ofdeionized water. This solution was recirculated across themicrofiltration membrane using the equipment described above. During thefiltration process 10,500 g of deionized water was added to the mainfeed tank at a rate that equaled the rate of permeate that was collectedon the other side of the microfiltration membrane. After the 10,500 g ofdeionized water was added and 10,500 g of permeate was collected, thesolution was allowed to recirculate in the microfiltration unit untilanother 3,685 g of permeate was collected. The sample was drained fromthe unit.

The final product had a solids content of 44.2%, particle size byBrookhaven BI-90 (light scattering) of 194 nm., and a Brookfieldviscosity (LVT viscometer, 30 rpm, 25° C.) of 68 cps.

Sample 24 was a control paint sample of JH2479 charged with DCPOEMA.Sample 25 was the diafiltered paint sample of JH2479 charged withDCPOEMA. Samples were stored at 140° F. for 10 days. The concentrationof DCPOEMA was measured by Gas Liquid Chromatography at 0, 5, and 10days storage. For this test, the reactive coalescent was consideredstable if greater than 50% of the reactive coalescent remained after 5and 10 days storage at 140° F. Preferred is greater than 60% of thereactive coalescent remaining after 5 and 10 days storage at 140° F.Most preferred is greater than 75% of the reactive coalescent remainingafter 5 and 10 days storage at 140° F. The results are shown in Table 5.

TABLE 5 Concentration of DCPOEMA in Coating Compositions Sam- 5 day @ 10day @ ple Polymer Initial 2 Week RT 140 F. 140 F. 24 JH2479 29,030 ppm28,200 ppm  2,600 ppm  1,365 ppm 25 Di- 28,875 ppm 27,863 ppm 24,982 ppm21,521 ppm afiltered

The results demonstrate that diafiltration of the polymer prior toformulation with DCPOEMA improves the stability of DCPOEMA in the wetcoating composition.

EXAMPLE 4 Analogs of DCPOEMA

Sample 26—Dicyclopentenyloxyethyl Butyrate

A solution of 155.2 grams (0.8 moles) of dicyclopentenyloxyethanol and201.5 grams (1.96 moles) of methyl butyrate was charged to a 500 ml,3-necked flask equipped with a thermometer, a mechanical stirrer, and a1 inch diameter-10 plate Oldershaw column fitted with a distillationhead, distillate rate removal—vapor temperature controller and agraduated distillate receiver. The solution was stirred and heated toreflux (108-112° C./700 mm of Hg). The water-methyl butyrate azeotrope(18.3 g) was distilled from the reaction mixture. At the conclusion ofthe dehydration, the solution was cooled to 60° C. and to it was added3.17 g (0.0056 moles) of tetraethylhexyl titanate. The reaction mixturewas heated to reflux (108° C./700 mm of Hg). The methanol ofreaction—methyl butyrate azeotrope was collected over a period of 4 ½hours. During the reaction the reaction temperature/pressure wasmaintained in the range of 108-123° C./700 mm of Hg. The progress of thereaction was monitored by Gas Liquid Chromatography (“GLC”) analysis ofthe reaction mixture, and by refractive index analysis of themethanol—methyl butyrate distillate. The reaction mixture was strippedof methyl butyrate at 72-122° C./400 mm of Hg to provide 209.5 g oforange liquid. By GLC analysis the stripped material contained 93.6 % ofdicyclopentenyloxyethyl butyrate.

Sample 27—Dicyclopentenvloxvethyl Acetate

A stirred reactor containing 58.1 g (0.30 moles) ofdicyclopentenyloxyethanol and 200 g (2.17 moles) of toluene was heatedto 41° C. A charge of 47.6 g (0.60 moles) of pyridine was added to thesolution over a period of 35 minutes followed by the addition of 34.8 g(0.435 moles) of acetyl chloride over a period of 1¾ hours. During theaddition of the pryidine and the acetyl chloride the reaction mixturetemperature was maintained between 42-47° C. The reaction mixture wasstirred and heated at 49-49.5° C. for 3¼ hours. The stirred reactionmixture was cooled to ambient temperature and to it was added 211 g ofwater and 100 g of toluene. The mixture was allowed to stand and thetoluene layer was isolated. The toluene solution was washed with 200 mlof water, isolated, stirred with 5 g of magnesium sulfate and gravityfiltered. The filtrate was stripped of toluene at reduced pressure toprovide 65.4 g of yellow liquid that contained 97.2%dicyclopentenyloxyethyl acetate by GLC analysis.

Sample 28—Dicyclopentenyloxyhexanol

A stirred reactor containing 116.2 grams (0.978 moles) of 1,6-hexanediolwas heated to 45° C. and sparged with nitrogen. A 3.0 gram (0.03 moles)solution of 95% sulfuric acid was added to the molten 1,6-hexanediol andthe mixture was heated to 110° C. Over a period of 3 ½ hrs. 99.7 grams(0.76 moles) of dicyclopentadiene was fed to the reaction mixture thatwas stirred and heated at 110-116° C. The reaction mixture was stirredand heated for 1.5 hrs. at 115° C. and was cooled to ambienttemperature. The mixture was allowed to stand at ambient temperature forseveral days. The mixture was stirred and to it was added 6.37 grams(0.08 moles) of 50% sodium hydroxide in water solution. The mixture wasfractionally vacuum distilled to obtain two water white distillationcuts of dicyclopentenyloxy hexanol. The amounts and analysis of each cutwas 56.7 grams of 88% dicyclopentenyloxyhexanol for product cut 1 and20.5 grams of 91.5% dicyclopentenyloxyhexanol for product cut 2. Thevapor temperature/vapor pressure at which the distillation cuts wereisolated was 195-202 ° C./10-12 mm. of Hg. The distillation cuts wereanalyzed by GLC.

The following analogs were prepared according to the proceduresdescribed above: dicyclopentenyloxy ethyl acetate, dicyclopentenyloxyethyl butyrate, dicyclopentenyloxy-2-(2-hydroxyethoxy)ethane,dicyclopentenyloxy-2-(2-butoxyethoxy)ethane, dicyclopentenyloxy hexanol,dicyclopentenyloxyhexane, dicyclopentenyloxybutane, dicyclopentenyloxy(2-methyl)propane, and 1,2-bis (dicyclopentenyloxy)ethane.

The analogs were tested for performance as reactive coalescents byincorporating them into coating compositions as follows:

thirty six g water, 3.21 g Tamol 165, 1.00 g Triton CF-10, 0.50 g DrewZV-22,

7.50 g Acrysol RM-2020NPR, and 90.00 g Ti-Pure R-700 were ground on ahigh speed disperser for 15 minutes. The following were added withcontinued mixing:

257.26 g HG-95, 0.50 g Drew ZV-22, 17.94 g DCPOEMA or DCPOEMA analog,6.21 g RM-202ONPR, and 77.83 g water. For the sample containing 1,2-bis(dicyclopentenyloxy)ethane, 35.88 g 1,2-bis (dicyclopentenyloxy)ethanewas added to the sample. The samples were tested for MFFT. The resultsare in Table 6.

TABLE 6 MFFT MFFT Coalescent Initial 10 Days @ 140 F. dicyclopentenyloxyethyl acetate  <5° C.  <5° C. dicyclopentenyloxy hexanol  5.4° C.  3.6°C. dicyclopentenyloxy ethyl butyrate  2.9° C.  1.6° C. 1,2-bis(dicyclopentenyloxy)ethane  4.2° C.  3.6° C. DCPOEMA  <5° C.   23° C.

The results indicate that the DCPOEMA analogs are more stable andtherefore perform better as reactive coalescents than DCPOEMA.

EXAMPLE 5 Oligomers of DCPOEMA

Sample 29

The materials of Table 7 were combined and sparged with N₂. Thissolution was pumped through a continuous reactor at 275° C. and 3500psi, with a flow rate such that its residence time was approximately 40seconds. The effluent solution was stripped of solvent and residualmonomer with a rotary evaporator, yielding a pale yellow oil. By GPC (inTHF vs. a polyMMA standard) M_(w)/M_(n)=2635/2111.

TABLE 7 material weight (g) ethyl acrylate 42 DCPOEMA 50 acrylic acid 8acetone 300 di t-butyl peroxide 1

Sample 30

The reactive coalescent sample was prepared by adding 2.76 grams ofaqueous ammonia (28%) to 40.00 grams of Sample 29. This modifed materialwas used as the reactive coalescent in the following formulation: 18.00g water, 1.61 g Tamol® 165, 0.50 g Triton® CF-10, 0.25 g Drew® ZV-22,3.75 g RM-202ONPR, and 45 g Ti-Pure® R-706 were ground with a high speeddisperser for 15 minutes. To this was added with continued stirring:131.27 g EXP-3361, 16.14 g reactive oligomer, 0.25 g Drew® ZV-22, 10.50g RM2020NPR, and 40.25 g water. The samples were tested for MFFT. Theresults are in Table 8.

TABLE 8 MFFT Coalescent Equilibrated 10 days @ 140 F. DCPOEMA 5.3°C. >18° C. Sample 30 (oligomer) 2.7° C.  3.9° C.

The results indicate that the DCPOEMA containing oligomers are morestable and therefore perform better as reactive coalescents thanDCPOEMA.

We claim:
 1. A composition comprising: from 1% to 25% of a vinylreactive coalescent based on a weight reactive coalescent to totalweight of composition basis; from 1 ppm to 10,000 ppm of an inhibitorselected from the group consisting of 4-methoxyphenol,4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy,4-oxo-2,2,6,6-tetramethyl- 1-piperidinyloxy, and di-tertiary butylnitroxyl, based on a weight inhibitor to total weight of compositionbasis; and from 74% to 99% of an emulsion polymer based on a weightemulsion polymer to total weight of composition basis.
 2. A compositionaccording to claim 1 wherein the vinyl reactive coalescent isdicyclopentenyloxyethylmethacrylate and the inhibitor is4-methoxyphenol.
 3. The compositon to claim 1 wherein the level of thevinyl reactive coalescent is in the range of 2% to 20%.
 4. Thecomposition according to claim 3 wherein the level of the vinyl reactivecoalescent is in the range of 5% to 15%.
 5. The composition according toclaim 1 wherein the level of the inhibitor is in the range of 100 ppm to1,000 ppm.
 6. The composition according to claim 5 wherein the level ofthe inhibitor is in the range of 200 ppm to 700 ppm.